Pyridyl-phosphorodithioic acid esters and methods of killing pests



3,304 226 PYRIDYL-PHOSPHOROIiITHIOIC ACID ESTERS AND METHODS OF KILLING PESTS Peter F. Epstein, El Cerrito, and Mervin E. Brokke, Rich- United States Patent 3,304,226 Patented Feb. 14, 1967 and water (100 parts) was stirred under reflux for 2 hours. The product that was isolated from the toluene layer by evaporation of the solvent was a white solid, M.P. 56- 58 C. The yield was 62.2 percent of theory.

5.5 mond Calif. assignors to Stauifer Chemical Company, 5 Y caiculated C12H17N2O2P2 4 6 H, 5.42, N, 8.85, S, 20.27, P, 9.79. Found. C, 45.79, H, New York, N.Y., a corporation of Delaware 5 37 N 8 S 20 P 10 01 N0 Drawing. Filed July 10, 1964, Ser. No. 381,927 1 1 1 4 Claims. (Cl. 167-33) Example 2 This invention relates to a certain new and novel class 0 Py i y y fy phosphoro diof phosphorous containing organic compounds and to the mlXtuYe P 213160191 Chloride Y 9 use of same as insecticides and acaricides. The com- P ammonium Q y Phosphorodlthloate pounds are particularly valuable for their insecticidal and P and Water Was heamd under reflux miticidal properties. More specifically, this invention refor 2 hOuYS- P baslficatlon the Product Was Obtalned lates to pyridine phosphates of the general formula hy "n The Yield Was percent 0 t eory.

0R1 Analysis.Calculated for C H NO PS C, 43.31; H, (CH1)..(SCz)mSP 5.81; N, 5.05; S, 23.12; P, 11.17. Found: C, 43.07; H,

/ 0R2 6.00; N, 4.98; S, 23.31; P, 11.28.

X l 20 Example 3 231/ s ,3 2 pyridyl) ethyl thiom'ethyl] 0,0 diwherein X is selected from the group consisting of hydrorh lhosphorodithioate. To a mixture of fi-(2-pyridyl)- gen, lower alkyl and eyano radicals and com'binaticfns ethane-thiol (13.9 parts),potassium hydroxide (5.6 parts), thereof, R1 and R2 are selected from the g p eensistlng ethanol (150 parts) and water (100 parts) was added sof lower y lower alkoxyalkyl and lower haloalkyl, m chloromethyl-0,0-diethylphosphorodithioate 23.5 parts). is an integer from 0 t0 and is an integer from The mixture was heated under reflux for 2 hours. After iIlClllSiVe- The invention includes a method of p p removal of potassium chloride and the solvent, the prodtion, utility and application of said compounds. uct was obtained as a pale brown oil, n =1.5568. The

Within the embodiment of the present invention, the yield was 70 percent of theory.

pyridine phosphates of the above-mentioned formula, An l i cal ul t d f C H NO PO C, 42,71; wherein n is the integer 3 and 4, are easily prepared by the H, 5.97; N, 4.15; S, 28.51; P, 9.18. Found: C, 4.40; H, method of Example 3 of the following examples using the 5.98; N, 4.12; S, 28.73; P, 8.74. corresponding w-(2-pyridyD- 1k thiOlp s of The following is a table of the compounds prepared Compounds t t ca b pr p r are When is -[v-'( according to one of the above described procedures, despyridyl),-propylthiomethyl] 0,0 diethyl-phosphorodiignated by the example number. Compound numbers thioate, and when n is 4, S-[w-(Z-pyridyl)-butylthiomethhave been assigned to each compound and are used yl]-0,0-diethyl-phosphorodithioate.' throughout the balance of the application.

TABLE I 0R (CH2)11(SOH2) SP Opd. Method of Position of M.P. or No. Preparation X Phosphate n 111 R1 and R1 n Substitution 1 3-CN, 4-Me, fi-Me 2 0 0 56-58 2 H, H, H 2 1 0 1. 5 4 3 H, H, H 2 2 1 1.5568 3 H, H, H 3 1 1 1. 5658 3 H, H, H 2 1 1 1,5628 3 H, H, fi-Me 2 1 1 1,5593 3 H, H, H 2 1 1 1.5601 3 H, H, H 2 2 1 1. 5499 3 H, H, H 4 2 1 1.5575 2 H, H, H 2 1 0 CZH4OCH3 1.5455 2 H, H, H 2 2 0 CZH4CL 1. 5542 1 Degrees eentigrade.

*No. 1 prepared in Example 1; No.

The compounds of the present invention can be made in accordance with the following illustrative examples.

7 Example 1 S (3 cyano 4,6 dimethyl 2 pyridyl) 0,0-

-diethylphosphorodithioate.A mixture of 2-chloro-3- cyano-4,6-dimethyl-pyridine (16.6 parts), potassium 0,0- diethyl phosphorodithioate (25 parts), toluene (100 parts) 2 prepared in Example 2; N o. 3 prepared in Example 3.

cidal activity. Young pinto bean plants in the primary leaf stage were used as the host plants. The young pinto bean plants were infested with several hundred mites. Dispersions of candidate materials were prepared by dissolving 0.1 gram in ml. of a suitable solvent,

- five insects were employed per cage.

taken after seventy-two hours.

a usually acetone. Aliquots of the toxicant solutions were The housefly evaluating tests differed in the following suspended in water containing 0.0l7S% v./v. Sponto manner. The toxicant was dissolved in a volatile sol- 22l, an emulsifying agent; the amount of water being vent, preferably acetone; the active compound was pisuflicient to give concentrations of active ingredient petted into a petri dish bottom, allowed to air dry and ranging from 0.25 to 0.003%. The test suspensions were 10 placed in a cardboard mailing tube. Twenty-five female then sprayed on the infested pinto bean plants. After flies, three to five days old, were caged inthe T111360 seven days, mortalities of adult and ovicidal forms were The flies were continuously exposed to the known residetermined. The percentage kill was determined by due of the active compound in the cage. After twentycomparison with control plants which had not been four and forty-eight hours counts were made to detersprayed with the candidates. The LD-SO value was mine living and dead insects. The LD-SO values were calculated using well known procedures. The LD-SO calculated using well-known procedures. The following values for two-spotted mite are reported under the 001- results were obtained.

TABLE II Insecticidal Activity Acaricidal Activity Compound 7 Number HF, g. AR, percent MWB PE E umns postembryonic (PE) and eggs (E) in Table II below.

Some of the compounds of the present invention exhibited systemic m-iticidal properties, Particularly, compounds number 3, 5 and 6 were active as systemic acaricides. The compounds were subjected to a test to evaluate the root absorption and upward translocation of the candidate. Again the two-spotted mite was employed in the test for systemic activity. Young pinto bean plans in-the primary leaf stage were used as the host plants. The plants were placed in bottles containing 200 ml. of the test solution and held in place with cotton plugs. Only the roots were immersed- The solutions were prepared by dissolving the compounds to be tested in a suitable solvent, usually acetone, and then diluting with distilled water. The final acetone concentration never exceeded 1%. The toXicants were initially tested at a concentration of 10 parts per million (p.p.'m.). Immediately after the plants were placed in the test solutions they were infested with mites. Mortalities were determinedafter seven days. The percentage of kill was determined by comparison with control plants which had been placed in distilled water only. The LD-SO value in ppm. were calculated and reported: compound number 3, 0.5 p.p.m., number 5, 0.75 p.p.m., and number 6, 3 ppm. 1

Insecticidal evaluation test-Three insect species were subjected to evaluation tests for insecticides incorporating the compounds of the present invention.

(1) HouseflyMusca domestica (Linn.)designated (2) American cockroachPeriplaneta americana (Linn.)desi gnated AR.

{3) Spotted milkweed bug-0nc0peltus fasciatus (Dal- 1as)designated MWB.

The procedure for the insects was similar to the .acaricidal testing procedures. Test insects were caged in cardboard mailing tubes 3% in diameter and 2 /8 tall. The mailing tubes were supplied with cellophane bottoms and coarse mesh nylon tops. Each cage was From these data it can be seen that these new compounds are valuable insecticides and acaricides. They may also he used in the form of emulsions, non-aqueous solutions, wettable powders, vapors, dusts, and the like, as may be best fitted to the particular utility. The application to a pest habitat of the compounds of the present invention are well known to those skilled in the art.

Various changes and modifications may be made without departing from the spirit and scope of the invention described herein as will be apparent to those skilled in the art to which it pertains. It is accordingly intended that the present invention shall only be limited by the scope of the appended claims.

We claim:

1. The method of killing pests selected from the group consisting of insects and acarids comprising applying to said pest habitat an effective amount of a compound of the formula s 03 T/ (OH2)n(SCHz) SP \0 R2 wherein R and R are lower alkoxy alkyl, m is an integer from 0 to 1 and n is an integer from 0 to 4, inelusive.

2. The method of killing pests selected from the group consisting of insects and acarids comprising applying to said pest habitat an effective. amount of 0,0bis(B- methoxyethyl) -S-( Z-pyridylmethyl -phosphorodithioate.

3. Compound of the formula (ornmsonnms 0R2 wherein R and R are lower alkoxy alkyl, m is an integer from 0 to 1 and n is an integer from 0 to 4, inelusive.

5 6 4. The compound, 0,0 bis 8 methoxyethyl) S-(2- FOREIGN PATENTS pyridylmet-hyl)-phosphomdithioate. 199,000 8/1958 Austria 713,278 8/1954 Great Britain. References Clted by the Exammer 13,079 7/1963 Japan.

UNITED STATES PATENTS 5 2,862,019 11/1958 Schrader 260-294.8 XR JULIAN S LEVI'IT, Primary Examiner, 2,961,445 11/1960 Saul 260-2948 3,041,367 6/1962 Leber et a1. 260294.8 XR VERA CLARKE Assistm Examine- 

1. THE METHOD OF KILLING PESTS SELECTED FROM THE GROUP CONSISTING OF INSECTS AND ACARIDS COMPRISING APPLYING TO SAID PEST HABITAT AN EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA 